Internal mold release compositions

ABSTRACT

Internal mold release compositions for use in preparing molded polymeric products are disclosed which contain (a) a primary or secondary amine, (b) a carboxylic acid or amido carboxylic acid salt of a group II metal or of aluminum, lithium, copper, iron, cobalt or nickel, and optionally (c) a carboxylic acid or amido caroxylic acid.

This is a divisional of application Ser. No. 570,141, filed Jan. 12,1984, now U.S. Pat. No. 4,876,019, issued Oct. 24, 1989, incorporatedherein by reference, which is a continuation-in-part of application Ser.No. 466,826, filed Feb. 16, 1983, now abandoned.

BACKGROUND OF THE INVENTION

The present invention pertains to internal mold release compositions andto polyol compositions containing same and process for preparingpolymeric products.

Polyether polyurethane moldings are being increasingly used in themanufacture of automobiles, furniture and in home construction. Moldedpolyether polyurethanes are especially important because they arelightweight and are resistant to moisture, weather, temperatureextremes, and aging. As an illustration, molded polyether polyurethaneelastomers have become of special interest in the manufacture offorce-reducing impact media such as safety impact bumpers for automotivevehicles and impact resistant automotive fascia.

The high demand for molded polyether polyurethane articles requires thatthey be produced in the largest numbers in the shortest possible time.Polyurethane-forming mixtures are eminently suited for mass productionbecause the reactants are liquid, that is they are pumpable, and arequick-reacting. The problem has existed, however, in providing adequatemold release in the shortest possible time to take fullest advantage ofthe unique capabilities of the polyurethane systems.

Heretofore, release of molded articles from molds in which they havebeen formed has been achieved by coating the surface of the mold cavitywith an agent which facilitates release of the molded article from thewalls of the mold cavity. Procedures such as this are described in U.S.Pat. Nos. 3,694,530; 3,640,769; 3,624,190; 3,607,397 and 3,413,390. Thismethod has certain disadvantages. The agent, after molding, adheres tothe surface of the molded article thereby removing such from the surfaceof the mold. As the mold release agent is removed from the mold surface,it must therefore be replaced so as to provide continued release of themolded articles from the mold. The necessity for repeated additions ofmold release agent results in higher costs due to low productivity as aresult of the additional time incurred in applying such additionalquantities of mold release agents to the mold surfaces.

In addition, mold build-up may become a problem, since a fine film ofurethane is left in spot areas of the mold surface. This build-up on thesurface of the mold cavity walls eventually covers and obscures anydetail on the mold cavity surface desired to be imparted to the moldedarticle. Also, the presence of the release agent adhering to the surfaceof the molded article can impede subsequent operations on the article,such as painting or adhering operations.

Additionally, the need to reapply the release agent after each moldingor a limited number of moldings interrupts the molding operation andslows down output.

The use of internal mold release agents for use in molding polyurethanearticles has been disclosed by Boden et al. in U.S. Pat. No. 3,726,952,Godlewski in U.S. Pat. No. 4,024,088, Bonin et al. in U.S. Pat. No.4,098,731, Sparrow et al. in U.S. Pat. No. 4,130,698, Godlewski in U.S.Pat. No. 4,111,861, Kleimann et al. in U.S. Pat. No. 4,201,847 andGodlewski in U.S. Pat. No. 4,220,727.

Some of these internal mold release agents bleed or creep to the surfaceof the molded article. Some of these articles cannot be painted evenafter appropriate preparation steps for painting has been done. Othersare incompatible with polyether polyols. Most of them seriously reducethe activity of the catalyst. Almost all show degradation of physicalproperties such as reduced elongation.

The use of the "salts" described in U.S. Pat. No. 3,726,952 have notbeen effective release agents for reaction injection molding (RIM).While showing release characteristics per se their use has demonstratedin a screening program wherein hand mixed formulations are cast into anopen mold other serious problems, namely: (1) degradation of the tincatalyst employed in the formulation, (2) excessively long gel and curetime, and (3) poor physical properties. These problems are believed tobe caused by the presence of free carboxylic acid. It is released fromthe salt by the reaction of the amine with the isocyanate, and it isbelieved that the presence of these free carboxylic acids, or any acid,interferes with the cure rate of the hydroxyl-isocyanate reaction toform a urethane structure as disclosed in J. Polymer Science, PolymerChemistry Edition, Vol. 19, 381-388 (1981) John Wiley & Son, Inc.

The reactivity or catalyst kill problem can be overcome to a certaindegree by using tertiary amines in place of primary or secondary amines.Both U.S. Pat. Nos. 3,726,952 and 4,098,731 describe this technique.Since isocyanates cannot react with tertiary amines the salt cannot besplit; it thus remains neutral (the carboxylic acid is not free), hence,catalyst kill does not seem evident. The use of tertiary amines,however, often shows bleed out or exudation problems which in turnresult in poor paint adhesion. Further, retention of physical propertiesis seldom possible because of either excess reactivity when using verycatalytically active amines, or because of plasticizer effects broughtabout by excessively long tertiary amine molecules.

The technology of U.S. Pat. No. 4,111,861 states that polar metalcompounds can be employed to overcome catalyst kill problems brought onby the presence of fatty carboxylic acids. It states that metal ionsmust be present in an amount sufficient to neutralize the acid.Reference is made to the use of the Bi, Pb, Na, Li, and K ion, withsodium carbonate, sodium oleate, and potassium laurate beingexemplified. They also show sodium oleate alone to be an effectiverelease agent. When evaluated in RIM polyol systems as a singleadditive, it failed to show adequate release characteristics in ascreening program wherein hand mixed formulations were cast into an openmold.

Zinc stearate has long been known to be an effective release agent formost thermoplastics. It is also used in polyester sheet moldingcompounds. When evaluated in RIM polyol systems containing only hydroxylgroups as the active hydrogen-containing source, zinc stearate as asingle additive failed to show adequate release characteristics in ascreening program wherein hand mixed formulations were cast into an openmold. Zinc stearate was observed to dissolve in a mixture of oleoylsarcosine and excess polyoxypropylene diamine of 400 MW and theresultant mixture performed as an effective mold release agent.

The present invention provides for an improvement in one or more of thefollowing: (1) increased multiple release, (2) increased ease ofrelease, (3) effective and very stable catalyst reactivity, and (4)minimally altered physical properties in molded parts.

SUMMARY OF THE INVENTION

One aspect of the present invention pertains to an internal mold releasecomposition which comprises

(A) at least one metal salt of an organic material derived from amaterial containing at least one carboxylic acid group,phosphorus-containing acid group or boron-containing acid group ormixture of such materials; wherein said metal is selected from Groups I,II, III-A, IV-B, V-B, VI-B, VII-B or VIII-B of the Periodic Table of theElements, Sn, Pb, Sb or Bi and wherein said organic material contains abackbone of siloxane chains or contains at least one terminal or pendantsaturated or unsaturated aliphatic hydrocarbon chain containing at leastabout 7 carbon atoms;

(B) a material containing at least one primary amine group and/or atleast one secondary amine group per molecule or a mixture of suchmaterials; and optionally

(C) at lease one organic material containing at least one carboxylicacid group, phosphorus-containing acid group or boron-containing acidgroup or mixture of such materials wherein said organic materialcontains a backbone of siloxane chains or contains at least one terminalor pendant saturated or unsaturated aliphatic hydrocarbon chaincontaining at least about 7 carbon atoms.

Another aspect of the present invention pertains to an activehydrogen-containing composition comprising

(I) at least one active hydrogen-containing material having a pluralityof either one or a combination of any two or more groups selected from--OH, NH, --NH and --SH; and

(II) an effective amount of internal mold release components to providea composition comprising the aforementioned internal mold releasecomposition.

Another aspect of the present invention pertains to a compositionsuitable for use as an internal mold release which composition comprises

(A) a metal salt of either a carboxylic acid or an amido-containingcarboxylic acid or a mixture of either or both wherein said metal is amember of Group II of the Periodic Table of Elements, aluminium,lithium, copper, iron, cobalt or nickel;

(B) a material containing at least one primary amine group and/or atleast one secondary amine group per molecule or a mixture of suchmaterials; and

(C) either a carboxylic acid or an amido-containing carboxylic acid or amixture of either or both; and wherein the components are employed inquantities such that

(i) the equivalent ratio of (C):(B) is from about 0.04:1 to about 2:1,preferably from about 0.08:1 to about 1.5:1; and

(ii) the weight ratio of (C):(A) is from about 0.3:1 to about 3:1,preferably from about 0.8:1 to about 1.2:1; with the proviso that atleast either

(1) at least one of the components (A) or (C) contains a terminal orpendant saturated or unsaturated aliphatic hydrocarbon chain having atleast about seven carbon atoms attached to a carbonyl group or

(2) component (B) contains a saturated or unsaturated aliphatichydrocarbon group having at least about seven carbon atoms attached to aprimary or secondary amine group.

Another aspect of the present invention pertains to an activehydrogen-containing composition comprising

(I) at least one active hydrogen-containing material having a pluralityof either one or a combination of any two or more groups selected from--OH, --NH, NH and --SH;

(II) an effective amount of an internal mold release composition whichcomprises

(A) a metal salt of either a carboxylic acid or an amido-containingcarboxylic acid or a mixture of either or both wherein said metal is amember of Group II of the Periodic Table of Elements, aluminium,lithium, copper, iron, cobalt or nickel;

(B) a material containing at least one primary amine group and/or atleast one secondary amine group per molecule or a mixture of suchmaterials; and

(C) either a carboxylic acid or an amido-containing carboxylic acid or amixture of either or both; and wherein the components are employed inquantities such that

(i) component (II-A) is employed in a quantity such that the weightratio of (II-C):(II-A) is from about 0.3:1 to about 3:1, preferably fromabout 0.8:1 to about 1.2:1; and

(ii) components (II-C) and (II-B) are employed in quantities whichprovide an equivalent ratio of (II-C):(II-B) of from about 0.04:1 toabout 2:1, preferably from about 0.08:1 to about 1.5:1; with the provisothat at least either

(a) at least one of the components (II-A) or (II-C) contains a terminalor pendant saturated or unsaturated aliphatic hydrocarbon chain havingat least seven carbon atoms attached to a carbonyl group or

(b) component (II-B) contains a saturated or unsaturated aliphatichydrocarbon group containing at least about seven carbon atoms attachedto a primary or secondary amine group.

Another aspect of the present invention pertains to an activehydrogen-containing composition which comprises

(I)(A) a relatively high equivalent weight active hydrogen-containingmaterial containing a plurality of hydroxyl groups, thiol groups,primary amine groups, secondary amine groups or combination of suchgroups or a mixture of such active hydrogen-containing materials;

(B) at least one relatively low equivalent weight activehydrogen-containing material having a plurality of at least one memberselected from --OH, --NH, NH or --SH groups or at least one each of anytwo or more of such groups; or

(C) mixture thereof; and

(II) an effective amount of an internal mold release composition whichcomprises

(A) a metal salt of a carboxylic acid or an amido-containing carboxylicacid or a mixture of either or both wherein said metal is a member ofGroup II of the Periodic Table of Elements, aluminum, lithium, copper,iron, cobalt or nickel;

(B) a material containing at least one primary amine group and/or atleast one secondary amine group per molecule or a mixture of suchmaterials; and

(C) a carboxylic acid, an amido-containing carboxylic acid or a mixtureof either or both; and wherein the components are employed in quantitiessuch that

(i)component (II-C) is employed in a quantity such that the weight ratioof (II-C):(II-A) is from about 0.3:1 to about 3:1, preferably from about0.8:1 to about 1.2:1; and

(ii)components (II-C) and (II-B) are employed in quantities whichprovide an equivalent ratio of (II-C):(II-B) of from about 0.04:1 toabout 2:1, preferably from about 0.08:1 to about 1.5:1; with the provisothat at least either

(a) at least one of the components (II-A) or (II-C) contains a saturatedor unsaturated aliphatic hydrocarbon chain having at least seven carbonatoms attached to a carbonyl group or

(b) component (II-B) contains a saturated or unsaturated aliphatichydrocarbon group containing at least about seven carbon atoms attachedto a primary or secondary amine group.

Another aspect of the present invention pertains to a compositionsuitable for use as an internal mold release system which compositioncomprises

(A) at least one organic material containing at least one carboxylicacid group, boron-containing acid group, or phosphorus-containing acidgroup and which contains a backbone consisting of saturated orunsaturated aliphatic hydrocarbon chains or siloxane chains wherein saidacid groups have been at least partially but may be completely reacted,complexed or associated with a metal from group II of the Periodic Tableof the Elements, aluminum, lithium, copper, iron, cobalt or nickel; and

(B) at least a sufficient quantity of a material containing at least oneprimary amine group and/or at least one secondary amine group permolecule or a mixture of such materials so as to solubilize at leastabout 0.1 percent by weight of component (A) in any liquid compositionin which said mold release system is employed;

and wherein at least one of components (A) and (B) contains at least onelipophilic group.

Another aspect of the present invention pertains to an activehydrogen-containing composition comprising

(A) at least one active hydrogen-containing material having a pluralityof either one or a combination of any two or more groups selected from--OH, --NH, NH and --SH; and

(B) at least one organic material containing at least one carboxylicacid group, boron-containing acid group or phosphorus-containing acidgroup and which contains a backbone consisting of saturated orunsaturated aliphatic hydrocarbon chains or siloxane chains wherein saidacid groups have been at least partially but may be completely reacted,complexed or associated with a metal from group II of the Periodic Tableof the Elements, aluminum, lithium, copper, iron, cobalt or nickel; and

if component (A) contains an insufficient quantity of a materialcontaining primary or secondary amine groups, then the composition alsocontains

(C) at least a sufficient quantity of a material containing at least oneprimary amine group and/or at least one secondary amine group permolecule or a mixture of such materials so as to solubilize at leastabout 0.1 percent by weight of component (B) in said activehydrogen-containing composition

and wherein at least one of components (B) or (C) contains at least onelipophilic group.

Another aspect of the present invention pertains to an activehydrogen-containing composition which comprises:

(A) a relatively high equivalent weight active hydrogen-containingmaterial terminated in hydroxyl, primary amine, secondary amine or thiolgroups or a combination of such groups or a mixture of such activehydrogen-containing materials;

(B) at least one relatively low equivalent weight activehydrogen-containing material having a plurality of either one or acombination of any two or more groups selected from --OH, --SH, NH and--NH groups;

(C) at least one material containing at least one carboxylic acid group,boron-containing acid group or phosphorus-containing acid group andwhich contains a backbone consisting of saturated or unsaturatedaliphatic hydrocarbon chains or siloxane chains wherein said acid groupshave been at least partially but may be completely reacted, complexed orassociated with a metal from group II of the Periodic Table of theElements, aluminum, lithium, copper, iron, cobalt or nickel; and

if either of components (A) or (B) either individually or collectivelycontain an insufficient quantity of a material containing primary and/orsecondary amine groups, then the composition also contains

(D) at least a sufficient quantity of a material containing at least oneprimary amine group and/or at least one secondary amine group permolecule or a mixture of such materials so as to solubilize at least 0.1percent by weight of component (C) in said active hydrogen-containingcomposition

and wherein at least one of components (C) and (D) contains at least onelipophilic group.

Another aspect of the present invention pertains to an activehydrogen-containing composition comprising:

(A) at least one active hydrogen-containing material having a pluralityof either one or a combination of any two or more groups selected from--OH, --NH, NH and --SH; and

(B) an effective amount, of an internal mold release composition whichcomprises:

(1) at least one metal salt of a carboxylic acid wherein there is asaturated or unsaturated hydrocarbon chain having at least about 7carbon atoms attached to the carbonyl group of said acid and whereinsaid metal is selected from Group II of the Periodic Table of theelements; and if component (A) contains an insufficient quantity ofprimary or secondary amine groups, then component (B) also contains

(2) at least one material containing at least one primary amine groupand/or at least one secondary amine group per molecule or a mixture ofsuch materials; and wherein

(i) the weight ratio of component (B-1) to the combined weight ofcomponents (A) and (B-2) is from about 0.001:1 to about 0.15:1,preferably from about 0.002:1 to about 0.1:1, most preferably from about0.004:1 to about 0.05:1;

(ii) the weight ratio of all compounds containing primary and/orsecondary amine groups to the combined weight of components (A) and(B-2) is from about 0.002:1 to about 1:1, preferably from about 0.003:1to about 0.5:1, most preferably from about 0.06:1 to about 0.22:1; and

(iii) component (B-1) is soluble in said composition to the extent of atleast about 0.1, preferably from about 0.5 to about 6, percent by weightof said active hydrogen-containing composition.

Another aspect of the present invention pertains to an activehydrogen-containing composition which comprises:

(I)(A) at least one relatively high equivalent weight activehydrogen-containing material terminated in hydroxyl, primary amine,secondary amine or thiol groups or a combination of such groups or amixture of such active hydrogen-containing materials;

(B) at least one relatively low equivalent weight activehydrogen-containing material having a plurality of either one or acombination of any two or more groups selected from --OH, --SH, NH and--NH groups; or

(C) mixture thereof; and

(II) an effective amount of an internal mold release composition whichis substantially soluble in said active hydrogen-containing compositionwhich comprises:

(A) at least one metal salt of a carboxylic acid wherein there is asaturated or unsaturated hydrocarbon chain having at least about 7,carbon atoms attached to the carbonyl group of said acid and whereinsaid metal is selected from Group II of the Periodic Table of theelements; and if component (A) contains an insufficient quantity ofprimary or secondary amine groups, then

(B) at least one material containing at least one primary amine groupand/or at least one secondary amine group per molecule or a mixture ofsuch materials; and wherein

(i) the weight ratio of component (II-A) to the combined weight ofcomponents (I) and (II-B) is from about 0.001:1 to about 0.15:1,preferably from about 0.002:1 to about 0.1:1, most preferably from about0.004:1 to about 0.05:1;

(ii) the weight ratio of all compounds containing primary and/orsecondary amine groups to the combined weight of components (I) and(II-B) is from about 0.002:1 to about 1:1, preferably from about 0.002:1to about 1:1, preferably from about 0.06:1 to about 0.22:1; and

(iii) component (II-A) is soluble in said composition to the extent ofat least about 0.1 percent by weight of the combined weight ofcomponents (I) and (II-B).

Another aspect of the present invention pertains to an improvement in aprocess for preparing polymeric products which process comprises mixingand injecting into a suitable mold a polyisocyanate and/orpolyisothiocyanate "A-side" component and an active hydrogen-containing"B-side" component wherein the improvement comprises employing as the"B-side" component, any of the aforementioned active hydrogen-containingcompositions.

The term polymer as employed herein means those polymers containingurethane and/or urea groups.

The term effective amount of an internal mold release as employed hereinmeans that quantity which will permit a molded part prepared fromreaction of the active hydrogen-containing composition with acomposition containing a plurality of --NCO and/or --NCS groups to beeasily removed from its mold.

The term total hydrogen equivalent weight as employed herein means themolecular weight divided by the total number of hydrogen atoms in themolecule which are connected to nitrogen, oxygen and sulfur atoms.

The term equivalent ratio as it pertains to the ratio of the acid saltcomponent and the amine component means the ratio of the number of##STR1## equivalents contained in the acid salt component to the numberof amine nitrogen equivalents contained in the amine component.

By the term lipophilic as employed herein it is meant that the materialcontains at least one member of the group consisting of R--CH wherein Ris a saturated or unsaturated aliphatic hydrocarbon group having atleast 6 carbon atoms.

Any reference herein to the Periodic Table of the Elements refers tothat published by Sargent-Welch Scientific Company as catalog numberS-18806, 1968.

DETAILED DESCRIPTION OF THE INVENTION

Suitable carboxylic acids which can be employed herein as a component inthe internal mold release composition include any saturated orunsaturated aliphatic or cycloaliphatic carboxylic acid or aromaticcarboxylic acid, preferably those carboxylic acids having from about 2to about 30, preferably from about 2 to about 18, carbon atoms.

Also suitable as carboxylic acids are those represented by the formula##STR2## wherein R is a hydrocarbyl group having from 1 to about 12carbon atoms.

Particularly suitable carboxylic acids include, for example, oleic acid,lauric acid, palmitic acid, stearic acid, mixtures thereof and the like.

Suitable carboxylic acids include amido-containing carboxylic acids suchas the reaction products of carboxylic acid halides containing fromabout 1 to about 30, preferably from about 2 to about 18, mostpreferably from about 5 to about 18, carbon atoms with an aminocarboxylic acid having from about 2 to about 4, preferably from about 2to about 3, carbon atoms per molecule.

Particularly suitable carboxylic acids include amido-containingcarboxylic acids such as those represented by the general formula##STR3## wherein R is a hydrocarbon or substituted hydrocarbon grouphaving from 1 to about 29, preferably from about 2 to about 17, carbonatoms; R' is hydrogen, an alkyl or hydroxyl substituted alkyl grouphaving from 1 to about 3 carbon atoms and R" is a divalent hydrocarbongroup having from 1 to about 3, preferably 1, carbon atoms, such as, forexample, oleoyl sarcosine, lauryl sarcosine, capryl sarcosine, oleoylglycine, octanol glycine, oleoyl hydroxyethyl glycine, mixtures thereofand the like. These amido carboxylic acids can be prepared by theSchotten-Baumann acylation reaction wherein an acyl halide is reactedwith an amino acid.

Suitable materials containing at least one carboxylic acid group andcontaining siloxane chains include those described by J. W. Keil in U.S.Pat. No. 4,076,695 which is incorporated herein by reference.

Suitable organic materials containing at least one phosphorus-containingacid group include, for example, monostearyl acid phosphate, cetyldihydrogen phosphate, monolauryl phosphate, decyl dihydrogen phosphate,monobutyl monodecyl ester of phosphoric acid, mixtures thereof and thelike.

Suitable organic materials containing at least one boron-containing acidgroup include, for example, dioctadecyl ester of boric acid, monododecylmono(phenylmethyl) ester of boric acid, monododecyl monophenyl ester ofboric acid, monoheptadecyl mono(phenylmethyl) ester of boric acid,monodecyl ester of boric acid, mixtures thereof and the like.

Suitable amines which can be employed herein as a component in theinternal mold release composition include any aliphatic, cycloaliphatic,or aromatic compound containing at least one primary or secondary aminegroup with those compounds having at least two primary and/or secondaryamine groups being especially preferred.

Suitable amine compounds include, for example, oleyl amine, coco amine,talloil amine, ethanolamine, diethyltriamine, ethylenediamine,propanolamine, aniline, mixtures thereof and the like.

Particularly suitable as the amine component in the internal moldrelease composition are these aliphatic amines enumerated later on asbeing low equivalent weight amine-containing active hydrogen-containingmaterials, and aromatic amines of relatively low molecular weight activehydrogen-containing materials also enumerated later on. Examples of suchparticularly suitable amines include the compounds of aminatedpolyoxyalkane glycols, hexamethylene diamine, diethylenetriamine, andhydrocarbyl substituted aromatic amines such as, for example,diethylenetoluenediamine.

Suitable carboxylic acid or amido carboxylic acid salts of metals whichcan be employed herein as a component in the internal mold releasecomposition include those containing the metal ions from group IImetals, lithium, copper, aluminum, iron, cobalt, and nickel. The organicportions of these compounds are suitably saturated or unsaturated havingfrom about 2 to about 30, preferably from about 2 to about 21 carbonatoms. Particularly suitable metal salts of carboxylic acids or amidocarboxylic acids include, for example, zinc stearate, zinc oleate, zincpalmitate, zinc laurate, calcium stearate, calcium oleate, calciumpalmitate, calcium laurate, magnesium stearate, magnesium oleate,magnesium laurate, magnesium palmitate, nickel stearate, nickel oleate,nickel palmitate, nickel laurate, copper stearate, copper oleate, copperlaurate, copper palmitate, zinc stearoyl sarcosinate, zinc oleoylsarcosinate, zinc palmitoyl sarcosinate, zinc lauroyl sarcosinate,calcium stearoyl sarcosinate, calcium oleoyl sarcosinate, calciumpalmitoyl sarcosinate, calcium lauroyl sarcosinate, magnesium stearoylsarcosinate, magnesium oleoyl sarcosinate, magnesium palmitoylsarcosinate, magnesium lauroyl sarcosinate, nickel stearoyl sarcosinate,nickel oleoyl sarcosinate, nickel palmitoyl sarcosinate, nickel lauroylsarcosinate, copper stearoyl sarcosinate, copper oleoyl sarcosinate,copper palmitoyl sarcosinate, copper lauroyl sarcosinate or mixturesthereof and the like.

Suitable carboxylic acid salts containing siloxane chains herein includethe Group II, aluminum, lithium, copper, iron, cobalt or nickel salts ofthe acids described in the aforementioned U.S. Pat. No. 4,076,695.

The partially or totally reacted, complexed or associated acid or amidoacids with the metals of Group II of the Periodic Table of the elements,aluminum, lithium, copper, iron, cobalt or nickel can be prepared byreacting such acids or amido acids with the appropriate quantity of acompound containing the metal such as a hydroxide or if the metal isabove hydrogen in the electromotive series, it can be reacted directlywith the acid or acid amide.

Also, mixtures of the acids and metal salts of the acids which areavailable commercially can be employed when partially reacted, complexedor associated materials are desired. Likewise commercially availablemetal salts of the acids or amido acids can be employed when the totallyreacted, complexed or associated materials are desired.

For purposes of the present invention, the total hydrogen equivalentweight is determined by dividing the molecular weight by all of thehydrogen atoms contained in any material derived from --OH, --NH and NHand --SH groups, regardless of whether or not the group reacts with anNCO or NCS group when preparing molded articles.

In some instances the quality of the metal salt of a carboxylic acid ormetal salt of an amido-containing carboxylic acid may affect theperformance of the internal mold release composition. This is believedto be particularly true with the use of zinc stearate in urethanereaction injection molding systems.

Suitable materials which can be employed herein as relatively highequivalent weight hydroxyl-, primary amine- or secondaryamine-containing materials include, for example, those hydroxyl and/oramine materials having an average hydrogen functionality of from 2 toabout 8, preferably from 2 to 4 and an average total hydrogen equivalentweight of from about 500 to about 5000, preferably from about 1000 toabout 3000.

Suitable relatively high equivalent weight hydroxyl-containing polyolswhich can be employed herein include, for example, those polyether andpolyester polyols which have an average hydroxyl functionality of fromabout 2 to about 8, preferably from about 2 to about 4 and mostpreferably from about 2 to about 3 and an average hydroxyl equivalentweight of from about 500 to about 5000, preferably from about 1000 toabout 3000 and most preferably from about 1500 to about 2500, includingmixtures thereof.

Suitable relatively high equivalent weight polyether polyols which canbe employed herein include those which are prepared by reacting analkylene oxide, halogen substituted or aromatic substituted alkyleneoxides or mixtures thereof with an active hydrogen-containing initiatorcompound.

Suitable such oxides include, for example, tetrahydrofuran, ethyleneoxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styreneoxide, epichlorohydrin, epibromohydrin, mixtures thereof and the like.

Suitable initiator compounds include water, ethylene glycol, propyleneglycol, butanediol, hexanediol, glycerine, trimethylol propane,pentaerythritol, hexanetriol, sorbitol, sucrose, hydroquinone,resorcinol, catechol, bisphenols, novolac resins, phosphoric acid,mixtures thereof and the like.

Also suitable as initiators for the relatively high equivalent weightpolyols include, for example, ammonia, ethylenediamine, diaminopropanes,diaminobutanes, diaminopentanes, diaminohexanes, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine,ethanolamine, aminoethylethanolamine, aniline, 2,4-toluenediamine,2,6-toluenediamine, diaminodiphenyloxide(oxydianiline),2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,1,3-phenylenediamine, 1,4-phenylenediamine, naphthylene-1,5-diamine,triphenylmethane-4,4',4"-triamine, 4,4'-di(methylamino)-diphenylmethane,1-methyl-2-methylamino-4-aminobenzene, 1,3-diethyl-2,4-diaminobenzene,2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene,1-methyl-3,5-diethyl-2,6-diaminobenzene,1,3,5-triethyl-2,6-diaminobenzene,3,5,3',5'-tetraethyl-4,4'-diaminodiphenylmethane and amine aldehydecondensation products such as the polyphenylpolymethylene polyaminesproduced from aniline and formaldehyde, mixtures thereof and the like.

Suitable polyester polyols which may be employed herein include, forexample, those prepared by reacting a polycarboxylic acid or anhydridethereof with a polyhydric alcohol. The polycarboxylic acids may bealiphatic, cycloaliphatic, aromatic and/or heterocyclic and may besubstituted (e.g., with halogen atom) and/or unsaturated. Examples ofcarboxylic acids of this kind include succinic acid; adipic acid;suberic acid; azelaic acid; sebacic acid; phthalic acid; isophthalicacid; trimellitic acid; phthalic acid anhydride; tetrahydrophthalic acidanhydride; hexahydrophthalic acid anhydride; tetrachlorophthalic acidanhydride; endomethylene tetrahydrophthalic acid anhydride; glutaricacid anhydride; maleic acid; maleic acid anhydride; fumaric acid;dimeric and trimeric fatty acids; such as oleic acid, which may be inadmixture with monomeric fatty acids, terephthalic acid dimethyl ester;terephthalic acid bisglycol ester and the like. Mixtures of such acidsor anhydrides may also be employed.

Examples of suitable polyhydric alcohols include ethylene glycol,1,2-propylene glycol; 1,3-propylene glycol; 1,4-, 1,2- and 2,3-butyleneglycol; 1,6-hexane diol; 1,8-octane diol; neopentyl glycol; cyclohexanedimethanol (1,4-bis-hydroxymethyl cyclohexane) 2-methyl-1,3-propanediol; glycerol; trimethylol propane; 1,2,6-hexane triol; 1,2,4-butanetriol; trimethylol ethane; pentaerythritol; quinitol; mannitol;sorbitol; methyl glycoside; diethylene glycol; triethylene glycol;tetraethylene glycol; polyethylene glycol; dipropylene glycol;polypropylene glycols; dibutylene glycol; polybutylene glycols and thelike. The polyesters may contain some terminal carboxyl groups. It isalso possible to use polyesters of lactones such as caprolactone, orhydroxy carboxylic acids such as hydroxy caproic acid.

Other suitable relatively high equivalent weight polyols which can beemployed herein include polymer-containing polyols such as, for example,those disclosed in U.S. Pat. No. Re. 29,118 (Stamberger), U.S. Pat. No.Re. 28,715 (Stamberger), U.S. Pat. No. Re. 29,014 (Pizzini et al.) andU.S. Pat. No. 3,869,413 (Blankenship et al.), Hoffman in U.S. Pat. No.4,394,491 and Hoffman et al. in U.S. Pat. No. 4,390,645 all of which areincorporated herein by reference.

Also suitable as the relatively high equivalent weight polyols are thethiol derivatives of the afore-mentioned polyols such that all or aportion of the hydroxyl or amine groups are replaced with --SH groups.

Suitable materials which can be employed herein as relatively lowequivalent weight active hydrogen-containing materials include one ormore of any such materials containing either hydroxyl groups, primaryamine groups, secondary amine groups or mixtures of such groups; suchmaterials having an average active hydrogen functionality of from about2 to about 16, preferably from about 2 to about 8 and an average activehydrogen equivalent weight of from about 15 to about 500, preferablyfrom about 32 to about 200 and when the active hydrogen atoms arederived only from OH groups then the maximum equivalent weight is about200.

Also suitable relatively high equivalent weight activehydrogen-containing materials are the products resulting from aminatingthe polyether and polyester polyols described above.

Suitable relatively low equivalent weight polyols which can be employedherein include, for example, ethylene glycol, propylene glycol,trimethylol propane, 1,4-butane diol, diethylene glycol, dipropyleneglycol, bisphenols, hydroquinone, catechol, resorcinol, triethyleneglycol, tetraethylene glycol, dicyclopentadienediethanol, glycerine, lowmolecular weight ethylene and/or propylene oxide derivatives ofglycerine, ethylenediamine, diethylenetriamine, mixtures thereof and thelike.

Suitable relatively low equivalent weight amine-containing activehydrogen-containing materials which can be employed herein include, forexample, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane,isophoronediamine, diethylenetriamine, ethanolamine,aminoethylethanolamine, diaminocyclohexane, hexamethylenediamine,methyliminobispropylamine, iminobispropylamine,bis(aminopropyl)piperazine, aminoethyl piperazine,1,2-diaminocyclohexane, polyoxyalkyleneamines,bis-(p-aminocyclohexyl)methane, triethylenetetramine,tetraethylenepentamine, mixtures thereof and the like.

Also suitable relatively low equivalent weight activehydrogen-containing materials are the aminated polyoxyalkylene glycolshaving an average amino hydrogen equivalent weight of from about 60 toabout 110.

Suitable also as the relatively low equivalent weight activehydrogen-containing materials are the thiol derivatives of theaforementioned materials wherein at least one of the hydroxyl or aminegroups has been replaced with an --SH group.

The term aliphatic amine as employed herein includes also thecycloaliphatic amines and heterocyclic aliphatic amines so long as theycontain at least one primary or secondary amine group.

Suitable aromatic amines which can be employed herein as a relativelylow molecular weight active hydrogen-containing material include, forexample, 2,4-bis(p-aminobenzyl)aniline, 2,4-diaminotoluene,2,6-diaminotoluene, 1,3-phenylenediamine, 1,4-phenylenediamine,2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,naphthalene-1,5-diamine, triphenylmethane-4,4',4"-triamine,4,4'-di(methylamino)diphenylmethane,1-methyl-2-methylamino-4-aminobenzene, polyphenylpolymethylenepolyamines, 1,3-diethyl-2,4-diaminobenzene, 2,4-diaminomesitylene,1-methyl-3,5-diethyl-2,4-diaminobenzene,1-methyl-3,5-diethyl-2,6-diaminobenzene,1,3,5-triethyl-2,6-diaminobenzene,3,5,3',5'-tetraethyl-4,4'-diaminodiphenylmethane,4,4'-methylene-bis(2,6-diisopropylaniline), mixtures thereof and thelike.

Suitable polyisocyanates include the organic aromatic polyisocyanates,aliphatic polyisocyanates or mixtures thereof.

Suitable organic aromatic polyisocyanates which can be employed hereininclude, for example, any such polyisocyanate having 2 or more NCOgroups per molecule such as, for example, 2,4-toluenediisocyanate,2,6-toluenediisocyanate, p,p'-diphenylmethanediisocyanate,p-phenylenediisocyanate, naphthalenediisocyanate, polymethylenepolyphenylisocyanates, mixtures thereof and the like.

Also suitable as organic aromatic and/or aliphatic polyisocyanates arethe prepolymers prepared from such polyisocyanates and compounds having2 or more active hydrogen atoms; as well as such polyisocyanates and/orprepolymers thereof which have been modified to contain uretonimine orcarbodiimide linkages.

Suitable organic aliphatic polyisocyanates include, in addition to thehydrogenated derivatives of the above-mentioned organic aromaticpolyisocyanates, 1,6-hexamethylenediisocyanate, isophoronediisocyanate,1,4-cyclohexyldiisocyanate, 1,4-bis-isocyanatomethylcyclohexane,mixtures thereof and the like.

Also suitable are the corresponding polyisothiocyanates.

Preferably, the cross-linker or chain extender component employed hereinis a combination comprising

(1) at least one member selected from the group consisting of

(a) hydroxyl-containing materials which are essentially free ofaliphatic amine hydrogen atoms, have an average OH functionality of fromabout 2 to 4 and have an average OH equivalent weight of from about 30to about 120 and

(b) aromatic amine-containing materials which are essentially free ofaliphatic amine hydrogen atoms and which contain at least two aromaticamine hydrogen atoms; and

(2) at least one aliphatic amine-containing material having at least oneprimary amine group, an average aliphatic amine hydrogen functionalityof from about 2 to about 16 and an average aliphatic amine hydrogenequivalent weight of from about 15 to about 500.

Most preferably, the cross-linker or chain extender component is acombination comprising components (1-b) and (2) such as, for example, acombination of an aminated polyoxypropylene glycol having an averagemolecular weight of about 400 and diethyltoluenediamine.

The polymers can be prepared either in the presence or absence of acatalyst. Those polymers prepared from amine-containing polyols do notusually require a catalyst although catalysts can be employed ifdesired. On the other hand, those polymers prepared from polyols whichdo not contain nitrogen atoms are prepared in the presence of acatalyst.

Suitable catalysts which may be employed herein include, for example,organo-metal compounds, tertiary amines, alkali metal alkoxides,mixtures thereof and the like.

Suitable organo-metal catalysts include, for example, organo-metalcompounds of tin, zinc, lead, mercury, cadmium, bismuth, antimony, iron,manganese, cobalt, copper, vanadium and the like such as, for example,metal salts of a carboxylic acid having from about 2 to about 20 carbonatoms including, for example, stannous octoate, dimethyltin dilaurate,dibutyltin dilaurate, dibutyltin diacetate, ferric acetyl acetonate,lead octoate, lead oleate, phenylmercuric propionate, lead naphthenate,manganese naphthenate, copper naphthenate, vanadyl naphthenate, cobaltoctoate, cobalt acetate, copper oleate, vanadium pentoxide, mixturesthereof and the like.

Suitable amine catalysts include, for example, triethylenediamine,triethylamine, tetramethylbutanediamine, N,N-dimethylethanolamine,N-ethylmorpholine, bis-(2-dimethylaminoethyl)ether, N-methylmorpholine,N-ethylpiperidine, 1,3-bis-(dimethylamino)-2-propanol,N,N,N',N'-tetramethylethylenediamine, mixtures thereof and the like.

Suitable alkali metal alkoxides which can be employed as catalysts forurethane formation include, for example, sodium ethoxide, potassiumethoxide, sodium propoxide, potassium propoxide, sodium butoxide,potassium butoxide, lithium ethoxide, lithium propoxide, lithiumbutoxide, alkali metal salts of polyols such as described in U.S. Pat.No. 3,728,308, mixtures thereof and the like.

Preferably, these urethane catalysts are in liquid form, but if they areinherently a solid at the application temperature, then they may bedissolved in an appropriate liquid, such as, for example, dipropyleneglycol or they may be dissolved or dispersed in one of the components.

The catalysts, when employed, can be employed in quantities of fromabout 0.001 to about 5, preferably from about 0.01 to about 1 part per100 parts of total polyol employed depending upon the activity of thecatalyst. Very weak catalysts could possibly be employed in quantitiesabove 5 parts per 100 parts of polyol.

If desired, the polyurethanes can be modified so as to containisocyanurate or thioisocyanurate groups by employing relatively high NCOor NCS to active hydrogen ratios, e.g., greater than about 1.5:1,preferably greater than about 2:1, and employing a trimerizationcatalyst. Suitable trimerization catalysts which can be employed hereininclude, for example, the zwitterions disclosed by Kresta and Shen inU.S. Pat. No. 4,111,914 and the tertiary amines, alkali metal salts oflower alkanoic acids, mixtures thereof and the like as disclosed in U.S.Pat. No. 4,126,741 (Carleton et al.) all of which are incorporatedherein by reference.

The zwitterions can also function as a catalyst for urethane formation,i.e., the NCX-OH reaction.

If desired, the densities of the polymers produced herein can be reducedby incorporating a blowing agent into the formulation. Suitable suchblowing agents are fully described in U.S. Pat. No. 4,125,487 and inU.S. Pat. No. 3,753,933 and so much of these patents as pertain toblowing agents is incorporated herein by reference. Particularlysuitable blowing agents include the low boiling halogenated hydrocarbonssuch as methylene chloride and trichloromonofluoromethane.

Another suitable method for reducing the density is by frothing byinjecting an inert gas into the mixture of urethane or otherpolymer-forming components. Suitable such inert gases include, forexample, nitrogen, oxygen, carbon dioxide, xenon, helium, mixturesthereof such as air and the like.

If desired, cell control agents can be employed, particularly whenpreparing foams or microcellular products of reduced density and/or toassist in paintability of the polyurethane. Suitable cell control agentswhich can be employed herein include silicone oils such as, for example,DC-193, DC-195, DC-197 and DC-198 commercially available from DowCorning Corp.; SF-1034, PFA-1635, PFA-1700 and PFA-1660 commerciallyavailable from General Electric Co.; L-520, L-5320 and L-5340commercially available from Union Carbide Corp.; and B-1048 commerciallyavailable from PH. Goldschmidt, AG., mixtures thereof and the like.

The polyurethanes and other polymeric products may additionally contain,if desired, coloring agents, fire-retardant agents, fillers, modifiersand the like.

Suitable liquid and solid modifiers include those disclosed anddescribed in U.S. Pat. Nos. 4,000,105 and 4,154,716 and so much thereofas pertains to suitable modifier substances are incorporated herein byreference. However, any such modifier described therein which fulfillsthe definition of any of the other components as described in thisapplication are not considered as modifiers but rather as one of thecomponents of the present invention.

Particularly suitable as the modifier or filler substances arefiberglass reinforcement fibers, particularly those having lengths offrom about 1/16 inch (0.16 cm) to about 1/2 inch (1.27 cm) and milledglass fibers having a maximum length of 1/16 inch (0.16 cm), 1/8 inch(0.32 cm) and 1/4 inch (0.64 cm) and the like. Other particularlysuitable fillers are mica, wollastonite, and the like.

The components which react to form the polymeric products can be shapedor formed into useful articles by injecting the reactive mixture intomolds which are capable of withstanding the exotherm of the polymerizingmass and are non-reactive with and are insoluble when in contact withthe liquid reactive mixture. Particularly suitable molds are those madeof metal such as aluminum, copper, brass, steel and the like. In someinstances non-metal molds can be employed such as those made of, forexample, polyethylene, polypropylene, polyethylene terephthalate,silicone elastomers and the like.

Particularly suitable injection methods for RIM applications includethose disclosed in a paper entitled "THE BAYFLEX 110 SERIES--THE NEWGENERATION OF RIM MATERIALS", by W. A. Ludwico and R. P. Taylorpresented at the SOCIETY OF AUTOMOTIVE ENGINEERS PASSENGER CAR MEETING,Detroit, Mich. Sept. 26-30, 1977; a paper entitled "THE PROPERTIES OFHIGH MODULUS RIM URETHANES", by R. M. Gerkin and F. E. Critchfieldpresented at the above meeting; British Patent No. 1,534,258 titled"PROCESS FOR THE PRODUCTION OF ELASTOMERIC POLYURETHANE-POLYUREA MOULDEDPRODUCTS HAVING A COMPACT SURFACE SKIN" and a book by F. Melvin Sweeneyentitled INTRODUCTION TO REACTION INJECTION MOLDING, Technomics, Inc.,1979.

When injecting a relatively rapid-setting blend into massive metalmolds, it may be necessary in order for the molded article to have goodsurface characteristics to preheat the molds to an appropriatetemperature so that the mold will not abstract the heat ofpolymerization from the reactive mass and inappropriately delay thesolidification time expected of a given formulation. On the other hand,thin wall metal molds could exhibit a minimal "heat sink" effect onrelatively large cross section castings and thus, these thin wall metalmolds may not require preheating.

We claim:
 1. A process for preparing polymeric products which processcomprises mixing and injecting into a suitable mold an "A-side"component comprising a polyisocyanate and/or polyisothiocyanate and a"B-side" component comprising at least one material containing at leastone primary and/or secondary amine groups per molecule or a mixture ofsuch materials, and a metal salt of an organic material containing atleast one boron-containing acid group; wherein said metal is selectedfrom Groups IIA and II-B of the Periodic Table of the Elements, Li, Cu,Al, Fe, Co, Ni and wherein said organic material contains a siloxanechain or at least one terminal or pendant saturated or unsaturatedaliphatic hydrocarbon chain containing at least about 7 carbon atoms. 2.The process of claim 1 wherein said "B-side" contains at least onematerial having hydroxyl, primary amine or secondary amine groups, anaverage active hydrogen functionality of from 2 to about 8 and anaverage total active hydrogen equivalent weight of from about 500 toabout
 5000. 3. The process of claim 2 wherein said "B-side" contains apolyether polyol having an average hydroxyl functionality of from about2 to about 4 and an average hydroxyl equivalent weight of from about1000 to about
 3000. 4. The process of claim 3 wherein said metal salt ispresent in an amount from about 0.5 to about 6 weight percent of said"B-side" component.
 5. The process of claim 4 wherein said materialcontaining at least one primary and/or secondary amine groups permolecule is a product resulting from aminating a material prepared byreacting an initiator compound having from 2 to about 4 reactivehydrogen atoms with propylene oxide, a combination thereof in any orderor a mixture thereof, said product having an average molecular weight offrom about 200 to about 6000, an aromatic diamine or mixture thereof. 6.The process of claim 5 wherein said metal is zinc, and said materialcontaining at least one primary and/or secondary amine groups permolecule is a mixture of diethyltoluenediamine and a product resultingfrom aminating a material prepared by reacting an initiator compoundhaving from 2 to about 4 reactive hydrogen atoms with propylene oxide.7. The process of claim 6 wherein said organic material containing atleast one boron-containing acid group is selected from the groupconsisting of dioctadecyl ester of boric acid, monododecylmono(phenylmethyl) ester of boric acid, monododecyl monophenyl ester ofboric acid, monoheptadecyl mono(phenylmethyl) ester of boric acid andmonodecyl ester of boric acid.
 8. The process of claim 6 wherein the"B-side" component further comprises at least one material containing atleast one carboxylic acid group, phosphorus-containing acid group orboron-containing acid group or mixture thereof.
 9. The process of claim2 wherein the "B-side" component further comprises at least one materialcontaining at least one carboxylic acid group, phosphorus-containingacid group or boron-containing acid group or mixture thereof.